ISBN: 3-540-63650-1
TITLE: Catalysis and Zeolites
AUTHOR: Weitkamp, Jens; Puppe, Lothar (Eds.)
TOC:

1 Synthesis of Aluminosilicate Zeolites 
and Related Silica-Based Materials 1 
Jean-Louis Guth and Henri Kessler 
1.1 Scope 1 
1.2 Introduction 1 
1.2.1 Structure, Composition, Nomenclature 1 
1.2.2 History of Zeolite Synthesis 4 
1.3 Theoretical Part 5 
1.3.1 Crystallogenesis 5 
1.3.1.1 Nucleation 5 
1.3.1.2 Crystal Growth 9 
1.3.1.3 Advancement of the Crystallization with Time 13 
1.3.1.4 Ostwald's Rule 14 
1.3.2 Zeolite Synthesis, Mechanism and Chemistry 16 
1.3.2.1 Presentation of the Synthesis System 16 
1.3.2.2 Framework T Elements 18 
1.3.2.3 Mineralizer and T Element Species in the Solution 20 
1.3.2.4 Templates 22 
1.4 Experimental Part 23 
1.4.1 Experimental Factors 23 
1.4.1.1 Nature of the Reactants 24 
1.4.1.2 Composition of the Reaction Mixture 25 
1.4.1.3 Preparation Procedure of the Reaction Mixture 25 
1.4.1.4 Aging 26 
1.4.1.5 Seeding 26 
1.4.1.6 Nature of the Reactor 26 
1.4.1.7 Crystallization Temperature 27 
1.4.1.8 Pressure 27 
1.4.1.9 Agitation 27 
1.4.1.10 Heating Time 27 
1.4.2 Review of Zeolites Obtained from Various Reaction Systems 28 
1.4.2.1 All-Silica Molecular Sieves (T = Si) 28 
1.4.2.2 (Si, Al) Systems with Inorganic Cations 28 
1.4.2.3 (Si, Al) Systems with Inorganic and Organic Templates 29 
1.4.2.4 (Si, Al) Systems with Organic Templates 29 
1.4.2.5 (Si, T^II) Systems, T^II = Be, Co, Cu, Zn 30 
1.4.2.6 (Si, T^III) Systems, T^III = B, Fe, Ga 31 
1.4.2.7 (Si, T^IV) Systems, T^IV = Ge, Ti, Zr 32 
1.4.2.8 Other Si-Based Systems  V, Cr and Mo in Tetrahedral 
Frameworks 32 
1.4.3 Synthesis of Some Selected Important Zeolites 33 
1.4.3.1 Zeolites with the LTA-Type Structure 33 
1.4.3.2 Zeolites with FAU-Type Structures and Polytypes 34 
1.4.3.3 Synthesis of Zeolite Beta 36 
1.4.3.4 Synthesis of Zeolite LTL 37 
1.4.3.5 Synthesis of Zeolites with the MAZ-Type Structure 37 
1.4.3.6 Synthesis of Zeolites with the MFI-Type Structure 38 
1.4.3.7 Synthesis of Zeolites with the MOR-Type Structure 41 
1.4.3.8 Synthesis of Zeolites with the OFF- and/or 
the ERI-Type Structure 42 
1.5 Synthesis of Other Selected Materials 44 
1.5.1 Titanosilicates with Mixed Octahedral-Tetrahedral Frameworks 44 
1.5.2 Synthesis of Mesoporous Aluminosilicates 45 
1.6 Activation of Zeolites 46 
References 46 
2 Phosphate-Based Zeolites and Molecular Sieves 53 
Johan A. Martens and Pierre A. Jacobs 
2.1 Introduction 53 
2.2 Structural, Synthetic and Physicochemical Concepts Relevant 
to Poro-tecto-phosphates 54 
2.2.1 AlPO_4 (GaPO_4) Topological Concept 54 
2.2.2 Al (Ga) Coordination Concept 56 
2.2.3 Template: Framework Stoichiometry Concept 60 
2.3 Rationalization of Properties of Poro-tecto-phosphates 
with Structural, Synthetic and Physicochemical Concepts 62 
2.3.1 Pore Size 62 
2.3.2 Thermal Stability 62 
2.3.3 Adsorption Properties 65 
2.3.4 Isomorphic Substitution 68 
2.3.5 Isomorphic Substitutions SM Ia, Ib and IIa Generating 
Framework Charges 71 
2.3.6 Isomorphic Substitutions Ic and IIb Generating Electroneutral 
Frameworks 73 
2.3.7 Si Incorporation According to SM III Generating Si 
and AlP Domains 74 
2.3.8 Si Incorporation According to Combinations of SM IIa 
and SM III Generating SiAl and SiAlP Domains 75 
References 76 
3 Modification of Zeolites 81 
Gnter H. Khl 
3.1 Ion Exchange of Zeolites 81 
3.1.1 Introduction and Theory 81 
3.1.2 Aqueous Ion Exchange 81 
3.1.2.1 Ion-Exchange Isotherms 84 
3.1.2.2 Experimental 86 
3.1.2.3 Thermochemistry of Ion Exchange 88 
3.1.3 Ion Exchange of Zeolites X and Y 88 
3.1.3.1 Univalent Ion Exchange 90 
3.1.3.2 Divalent Ion Exchange 93 
3.1.3.3 Trivalent Ion Exchange 98 
3.1.4 Ion Exchange of ZSM-5 100 
3.1.4.1 Univalent Ion Exchange 100 
3.1.4.2 Divalent Ion Exchange 102 
3.1.4.3 Trivalent Ion Exchange 103 
3.1.4.4 Aluminum-Independent Ion Exchange 103 
3.2 Metals Supported on Zeolites 104 
3.2.1 Reduction of Metal Ions in Zeolites 105 
3.2.1.1 Group IB 105 
3.2.1.2 Group VIIIA, Fourth Period 113 
3.2.1.3 Group VIIIA, Fifth Period 116 
3.2.1.4 Group VIIIA, Sixth Period 123 
3.3 Dealumination of Zeolites 127 
3.3.1 Thermal Treatment 127 
3.3.1.1 Hydrogen Zeolites 128 
3.3.1.2 Dehydroxylation 132 
3.3.2 Extraction of Framework Aluminum with Acid 133 
3.3.2.1 The Aluminum-Deficient Form 134 
3.3.2.2 Annealing of Tetrahedral Vacancies; High-Silica Faujasite 135 
3.3.3 Hydrothermal Treatment 136 
3.3.3.1 The Stabilized Form 136 
3.3.3.2 The Ultrastable Form 140 
3.3.3.3 Dealumination of High-Silica Zeolites 142 
3.3.4 Direct Replacement of Aluminum with Silicon 145 
3.3.4.1 Reaction with Silicon Halides 145 
3.3.4.2 Reaction with Hexafluorosilicates 151 
3.3.5 Removal of Other Framework Elements 154 
3.4 Insertion into the Zeolite Framework 155 
3.4.1 Reinsertion of Hydrolyzed Aluminum 155 
3.4.2 Reaction with Aluminum Compounds 157 
3.4.2.1 Aqueous Aluminate 157 
3.4.2.2 Aluminum Oxide 158 
3.4.2.3 Aluminum Halides 161 
3.4.2.4 Complex Aluminum Fluoride 163 
3.4.2.5 Generation of Vacancies Prior to Alumination 163 
3.4.3 Insertion of Other Elements 164 
3.4.3.1 Group IIIA Elements 165 
3.4.3.2 Elements of Other Groups 167 
3.5 Other Modifications 169 
3.5.1 Reactions of OH-Groups 169 
3.5.1.1 Reaction with Silanes 170 
3.5.1.2 Reaction with Phosphines 172 
3.5.2 Reaction with Oxoacids 174 
3.5.2.1 Reaction with Derivatives of Phosphorous Acid 174 
3.5.2.2 Reaction with Phosphoric Acid 175 
References 179 
4 Characterization of Zeolites  Infrared and Nuclear 
Magnetic Resonance Spectroscopy and X-Ray Diffraction 198 
Hellmut G. Karge, Michael Hunger, and Hermann K. Beyer 
List of Abbreviations 198 
Introduction 199 
4.1 IR Spectroscopy 201 
4.1.1 Introduction 201 
4.1.2 Theoretical Background 201 
4.1.3 Experimental Techniques 204 
4.1.3.1 Transmission IR Spectroscopy 204 
4.1.3.2 Diffuse Reflectance IR (Fourier Transform) 
Spectroscopy (DRIFT) 206 
4.1.3.3 Photoacoustic IR Spectroscopy (PAS) 207 
4.1.3.4 Cells for Studying Zeolites and Zeolite Adsorbate Systems 
by IR Spectroscopy 208 
4.1.4 Study of Framework Vibrations of Zeolites 211 
4.1.5 IR Investigation of Acidic and Basic Sites in Zeolites 215 
4.1.5.1 Brnsted Acid Sites (Acidic Hydroxyls) 216 
4.1.5.2 Lewis Acid Sites  True Lewis Sites 230 
4.1.5.3 Lewis Acid Sites  Cations 231 
4.1.6 Basic Sites (Basic Hydroxyls, Basic Oxygens) 233 
4.1.7 Zeolite-Adsorbate Systems 235 
4.1.8 Motion, Diffusion and Reaction of Guest Molecules in Zeolites 238 
4.2 NMR Spectroscopy 239 
4.2.1 Introduction 239 
4.2.2 Theoretical Background 240 
4.2.2.1 Zeeman Interaction and Relaxation Effects 240 
4.2.2.2 Solid-State Interactions 242 
4.2.3 Experimental Techniques 245 
4.2.3.1 Methods of High-Resolution Solid-State NMR 245 
4.2.3.2 Cross-Polarization and Other Selected Pulse Techniques 248 
4.2.3.3 Two-Dimensional NMR Spectroscopy 249 
4.2.4 Applications 250 
4.2.4.1 29 Si MAS NMR Spectroscopy of SiO4 Tetrahedra 
in the Zeolite Framework 250 
4.2.4.2 27 Al NMR Spectroscopy of Framework 
and Non-Framework Aluminum in Zeolites 256 
4.2.4.3 31 P MAS NMR Spectroscopy of PO_4 Tetrahedra 
in Aluminophosphate-, Silicoaluminophosphate-, 
and Gallophosphate-Type Zeolites 262 
4.2.4.4 11 B MAS NMR Spectroscopy of Boron-Modified Zeolites 266 
4.2.4.5 Solid-State 17 O NMR Spectroscopy of the Zeolite Framework 266 
4.2.4.6 1 H MAS NMR Spectroscopy of Acidic and Non-Acidic 
Hydroxyl Groups in Zeolites 267 
4.2.4.7 Solid-State 23 Na NMR Spectroscopy of Sodium Cations 
in Hydrated and Dehydrated Zeolites 275 
4.2.4.8 133 Cs MAS NMR Spectroscopy of Cesium Cations 
in Hydrated and Dehydrated Mordenites and Faujasites 282 
4.2.4.9 129 Xe NMR Investigations of the Zeolitic Pore Architecture 285 
4.2.4.10 Investigations of Brnsted and Lewis Acid Sites 
by Probe Molecules 291 
4.3 Application of Powder X-Ray Diffractometry 
in Zeolite Research 295 
4.3.1 Introduction 295 
4.3.2 Parameters Affecting the Intensity of Bragg Reflections 296 
4.3.3 Calculation of Structure Factors 299 
4.3.4 Powder-Data Structure Refinement 302 
4.3.4.1 Profile-Fitting Method 303 
4.3.4.2 Rietveld Method 304 
4.3.4.3 Application of the Rietveld Method in Zeolite 
Structure Analysis 306 
4.3.5 Crystallinity Determination 308 
4.3.6 Determination of Framework Aluminum from X-Ray Data 310 
4.3.7 Determination of the Crystallite Size 314 
References 316 
5 Shape-Selective Catalysis in Zeolites 327 
Jens Weitkamp, Stefan Ernst, and Lothar Puppe 
5.1 Scope 327 
5.2 Introduction 328 
5.2.1 Molecular Dimensions 328 
5.2.2 Porous Solids: Crystallographic and Effective Pore Diameter 329 
5.2.3 Molecular Sieving 331 
5.3 Catalysis and Selectivity 333 
5.3.1 Incentives for Applying a Catalyst 333 
5.3.2 Intrinsic, Grain and Reactor Selectivity 334 
5.3.3 Shape-Selective Catalysis 335 
5.4 Internal vs. External Surface of Zeolites 336 
5.4.1 Effect of the Crystallite Size 336 
5.4.2 Experimental Techniques 337 
5.5 Examples for Shape-Selective Reactions and Models 
for Rationalizing the Observed Effects 340 
5.5.1 Early Observations 340 
5.5.2 The Classical Concept After Weisz and Csicsery 341 
5.5.2.1 Mass Transfer Effects: Reactant and Product Shape Selectivity 341 
5.5.2.2 Intrinsic Chemical Effects: Restricted Transition 
State Shape Selectivity 343 
5.5.2.3 Discrimination Between Mass Transfer 
and Intrinsic Chemical Effects 344 
5.5.3 Other Concepts 345 
5.5.3.1 The Cage or Window Effect 345 
5.5.3.2 Molecular Traffic Control 346 
5.5.3.3 Shape Selectivity at the External Surface: The Nest Effect 347 
5.5.3.4 Tip-on Adsorption of Molecules Diffusing Inside 
the Pore System 349 
5.5.3.5 Secondary Shape Selectivity/Inverse Shape Selectivity 350 
5.6 Tailoring the Shape-Selective Properties of Zeolite Catalysts 351 
5.6.1 Variation of the Zeolite Type and Isomorphous Substitution 351 
5.6.2 Variation of the Crystallite Size and Compositional Zoning 353 
5.6.3 Ion Exchange and Pore Size Engineering 354 
5.6.4 Selective Poisoning of the External Surface 355 
5.7 Catalytic Test Reactions for Probing the Effective Pore Width 
of Microporous Materials 356 
5.7.1 Test Reactions for Acidic Molecular Sieves 357 
5.7.1.1 Competitive Cracking of n-Hexane and 3-Methylpentane 
(the Constraint Index, CI) 357 
5.7.1.2 Isomerization and Disproportionation of meta-Xylene 359 
5.7.1.3 Reactions of Other Alkyl Aromatics 360 
5.7.2 Test Reactions for Bifunctional Molecular Sieve Catalysts 361 
5.7.2.1 Isomerization and Hydrocracking of Long-Chain n-Alkanes 
(the Refined or Modified Constraint Index, CI*) 362 
5.7.2.2 Hydrocracking of Butylcyclohexane 
(the Spaciousness Index, SI) 364 
5.8 More Recent Directions and Challenges 
in Shape-Selective Catalysis 365 
5.8.1 Trend Towards Bulkier Molecules 365 
5.8.2 Shape-Selective Catalysis on Transition Metals in Zeolites 367 
5.8.3 Stereoselective Catalysis in Zeolites 367 
5.8.4 Host/Guest Chemistry in Zeolites 368 
References 370 
6 Zeolite Effects in Organic Catalysis 377 
Patrick Espeel, Rudy Parton, Helge Toufar, Johan Martens, 
Wolfgang Hlderich, and Pierre Jacobs 
6.1 Reported Catalytic Technology with Zeolites 377 
6.2 Generalities on Catalytic Organic Chemistry with Zeolites 379 
6.3 Established Generalities on Shape Selectivity with Zeolites 382 
6.4 Generation of Active Sites in Zeolites 388 
6.5 The Latest Visions on Zeolite Acidity 393 
6.6 Zeolite Superacidity 397 
6.7 Zeolite Specificity in Organic Catalysis with Functional 
Molecules: Zeolite Effects 398 
6.7.1 Zeolite Effect I: Shape Selectivity 398 
6.7.1.1 General Procedures 399 
6.7.1.2 Manifestation of Shape Selectivity in Organic Reactions 400 
6.7.2 Zeolite Effect II: Specific Adsorption 409 
6.7.2.1 Diels-Alder Cycloadditions 409 
6.7.2.2 Friedel-Crafts Alkylation 409 
6.7.2.3 Beckmann Rearrangement 410 
6.7.3 Zeolite Effect III: Functional Selectivity 411 
6.7.3.1 Hydrogenation of Unsaturated Aldehydes 411 
6.7.3.2 Preparation of Allyl-Substituted Aromatics 
by Friedel-Crafts Methods 411 
6.7.4 Zeolite Effect IV: Multifunctional Synergy 412 
6.7.4.1 Hydrogenation + Alkylation 412 
6.7.4.2 Hydrolysis + Hydrogenation 413 
6.7.4.3 Hydration + Dehydrogenation 413 
6.7.4.4 Isomerization + Dehydrogenation 413 
6.7.4.5 Complete Process Changes by Zeolite Catalysts: 
epsilon-Caprolactam Production 413 
6.7.5 Zeolite Effect V: New Chemistry with Zeolites 414 
6.7.5.1 Pseudo-Solid-Solvent Effect 414 
6.7.5.2 New Complexes Through Encapsulation 414 
6.7.5.3 Ti-Zeolites 415 
6.8 Case Study: Zeolites as Non-Corrosive, Environmentally 
Friendly Friedel-Crafts Alkylation Catalysts 416 
6.8.1 Introduction 416 
6.8.2 Friedel-Crafts Chemistry over Zeolites 
from a Historical Perspective 417 
6.8.3 Overview of Friedel-Crafts Literature with Zeolites 417 
6.8.3.1 Group 1 Reactions: Alkylation of Alkyl Aromatics 
with Olefins 417 
6.8.3.2 Group 2 Reactions: Alkylation of Alkyl Aromatics 
with Alcohols, Ethers, Aldehydes, Amines etc. 420 
6.8.3.3 Group 3 Reactions: Alkylation of Heteroatom-Substituted 
Aromatics with Olefins 422 
6.8.3.4 Group 4 Reactions: Alkylation of Heteroatom-Substituted 
Aromatics with Alcohols, Aldehydes, Haloalkanes etc. 424 
6.8.4 Recent Developments in Friedel-Crafts Alkylation: 
Solvent Effects 427 
References 429 
7 Zeolites as Catalysts in Industrial Processes 437 
P.M.M. Blauwhoff, J.W. Gosselink, E.P. Kieffer, 
S.T. Sie, and W.H.J. Stork 
7.1 Introduction and General Overview 438 
7.1.1 Oil Refining: Basics 438 
7.1.2 The Petrochemical Industry 443 
7.2 Fluid Catalytic Cracking 444 
7.2.1 Feedstocks and Products 446 
7.2.2 Application of Fluid Catalytic Cracking (FCC) 451 
7.2.3 Reaction Mechanism 453 
7.2.4 The FCC Catalyst 455 
7.2.4.1 Catalyst Constituents 455 
7.2.4.2 Effect of Metals on FCC Catalyst Behavior 459 
7.2.4.3 Novel Zeolites in FCC Catalysts 459 
7.2.4.4 Physical Catalyst Parameters 460 
7.2.4.5 Mechanical Aspects 461 
7.3 Hydrocracking 461 
7.3.1 Process Configurations 462 
7.3.2 Feedstocks and Products 465 
7.3.3 Application of Hydrocracking 467 
7.3.4 Catalytic Aspects 469 
7.3.4.1 Hydrocracking Mechanism and "Ideal Hydrocracking" 469 
7.3.4.2 Hydrogenation Function 471 
7.3.4.3 Acidic Function 472 
7.3.4.4 Hydrocracking Catalysts 477 
7.3.5 Challenges in Hydrocracking 478 
7.4 Catalytic Dewaxing 479 
7.4.1 Introduction 479 
7.4.2 Principles of Catalytic Dewaxing 480 
7.5 Upgrading of Naphtha and Tops 484 
7.5.1 Cracking of Normal Paraffins 484 
7.5.2 Desulfurization of Naphtha ex Fluid Catalytic Cracking 486 
7.5.3 Isomerization of Light Paraffins 486 
7.5.3.1 Isomerization over Amorphous Catalysts 488 
7.5.3.2 Isomerization over Zeolitic Catalysts 491 
7.5.4 Isomerization of Light Olefins 492 
7.5.5 Paraffin/Olefin Alkylation 492 
7.5.6 Zeolite-Supported (De)Hydrogenation Catalysts 494 
7.5.6.1 Aromatization Catalysts 494 
7.5.6.2 Sulfur-Tolerant Hydrogenation Catalysts for Production 
of Low Aromatics Diesel 496 
7.6 Zeolites in Synfuels Production 496 
7.6.1 Conversion of Methanol to Gasoline (MTG) 496 
7.6.1.1 Reaction Mechanism 496 
7.6.1.2 The Fixed-Bed MTG Process 497 
7.6.1.3 The Fluid-Bed MTG Process 501 
7.6.2 Integration of Methanol Synthesis and Methanol 
Conversion (TIGAS Process) 502 
7.6.3 Direct Conversion of Synthesis Gas into Gasoline 505 
7.6.4 Conversion of Methanol to Synfuels via Light Olefins 506 
7.6.4.1 Methanol to Light Olefins (MTO) Process 507 
7.6.4.2 Light Olefins to Gasoline and Distillates (MOGD) Process 509 
7.6.5 Upgrading of Fischer-Tropsch Products with Zeolites 510 
7.6.6 Aromatics from Light Paraffins (Cyclar Process) 512 
7.7 Application of Zeolites in the Chemical Industry 513 
7.7.1 Introduction 513 
7.7.2 Acid-Catalyzed Reactions Giving Hydrocarbon Products 514 
7.7.2.1 Ethylbenzene from Benzene plus Ethylene 514 
7.7.2.2 Isopropylbenzene (Cumene) from Benzene plus Propylene 516 
7.7.2.3 Higher Alkylbenzenes 517 
7.7.2.4 p-Ethyltoluene from Toluene plus Ethylene 517 
7.7.2.5 Alkylation of Binuclear Aromatics 518 
7.7.2.6 Xylenes Production: Isomerization (Including Ethylbenzene) 
and Toluene Disproportionation 518 
7.7.3 Oxidation and Ammoximation Processes 522 
7.7.3.1 Hydroxylation of Phenol with Hydrogen Peroxide 523 
7.7.3.2 Epoxidation of Propylene 525 
7.7.3.3 Ammoximation of Cyclohexanone 525 
7.7.4 Amination 526 
7.8 Concluding Remarks 528 
References 530 
Subject Index 539 
END
